Tetrakisazo dyestuffs



Patented Mar. 11, 1941 UNITED STATES PATENT OFFICE TETRAKISAZO DYESTUFFSChiles E. Sparks, Wilmington, DeL, asslgnor to E. I. du Pont de Nemours& Company, Wilmington, Del., a corporation of Delaware No Drawing.Application September 12, 1939, Serial No. 294,419

14 Claims. (Cl. 8-46) This invention relates to direct tetrakisazo dyesstantive to cotton and other similar dye susof the type A Y*X Y Awherein X is the ceptible materials, such as regenerated celluloseradical of any diamino phenoxy compounds fibers. Another object of theinvention is to represented generally by the formula provide'new shadesin such direct tetrakisazo- HN NH2 dyes which give d eiriizgs havinggood brightness, 5

superior was ing as ness, moderate light fast- 2 'fi 'fi' ness and othersatisfactory characteristics. An-

0 0 I I other object of the invention is to provide tetra-' R kisazodyes which can be applied by simple lo the Y's are radicals of a class oall/183111165 Whlch economical methods and will give constant shade 10ar apa of a tin as up in components, and superior washing fastness.Other objects of and the As are radicals f i y y Compounds the inventionwill be apparent from the following of the benzene series. In theradical of X, M description. occurs twice in each radical and each BDThe objects of the invention are attained in sents members o a o pconsisting of hydrogeneral-by providing direct tetrakisazo dyes of genand alkyl, and m is an integer 1 to 10. The t type -xhi h are made by yb D represents radicals of a Class Of diamino diazotization of suitableprimary aryl amines and and di-imino compounds hereinafter to beexcoupling t t bl coupling compounds in t plained. These dyes arevaluable direct dyes for manner indicated by t above fgrmula In cottonand similar cellulosic substances. They general one of a, class offlaming djarylene c0111.. P e dyeings in b g t s a Superior pounds X istetrazotized and coupled with a washing fastness without loss of b ig tss suitable compound Y, eventually resulting in marked change of shadecanbe attained by formingadiS3ZOCOmpO1lI1dHzN-Y(X)Y NI-Ig after-t e thedyeings with or a y This compound is tetrazotized and then coupled thusproviding a class of dyes with which direct th th compound A forming-xdyeings on cotton can be made by employing In the formula A representsa dihydroxy com- Simple and economical methods and by means pound of thebenzene series having a formula of which dyeings in bright shades havingsuperior 0H washing fastness and moderate light fastness are 1 Iproduced. 0H 30 Direct colors for cotton and similar fibers which giveeven dyeings and have good bright- R ness with good washing fastness aredesired by the art. Direct tetrakisazo colors which are substantive tocotton but which are fugitive to washing, showing considerable loss instrength and imparting an undesirable stain in washing to un dyedassociated fibers are known. Tetrakisazo combinations which are made byazotizing a direct dyeing and developing on the fiber with suitablecoupling compounds .are also known. The latter colors are in generalduller in shade in which R is one of a group consisting of hydrogen,straight and branched chain alkyl having 35 1 to 6 carbons, alkoxy inwhich the alkyl portion is of like structure and number of carbons asalkyl, hydroxy, amino, CN, halogen, sulfonic acid and carboxyl.

Y is a compound capable of being coupled to 40 a diazotized aryl amineand having a diazotizable amino group when coupled and is from the groupthan direct colors and they are more costly to consisting of types ofanfino phenyl pymzolones' produce than direct colors by. reason of theamin naPht1{a1enes, ammo benzenes and ammo various operations incidentalto azotization of a naphthols whlch are represented by formulas as 45direct dyeing and subsequent development on the followsfiber. A changein shade usually resulting dur- The aryl compounds 0f h benzene ing suchadevelopmentissometimes inconvenient f have an open Position-forcoupling for the dyer where shades are to be duplicated. heated by Parato amino and are represente It is therefore desirable to provide directcolors y the formula 50 having bright shades and superior washingfastness which will produce dyeings economically l H: and conveniently.

It is among the objects of this invention to provide direct tetrakisazodyes which are sub in which R3 is one or more than one of any com 55bination. of the group consisting of hydrogen, alkyl and alkoxy. 1,

(2) The l-naphthylamines in which --H represents an open position forcoupling are represented by the formula in which R4 is one or more thanone of any combination of the group consisting of hydrogen,

alkyl, alkoxy, halogen, sulfonic acid and carboxyl.

(3) The 1-v and 2-amino naphthols represented by the formulae in whichR5 is one of a group consisting of hydrogen and sulfonic acid and -OHand SOaH are separated by at least one unsubstituted position, Z isamino or amino benzoyl amino of the formula containing not more than twobenzene nuclei and having one primary amino group meta or para to a COgroup, and Re is one of a group consisting of sulfonic acid andcarboxyl. As illustrations of Z radicals, those represented by theformulae I Rs 4 and NHCO --NHCO v l are mentioned.

(4) The 1(aminophenyl) pyrazolones which have amino in the meta or paraposition of the benzene nucleus and are represented by the formula inwhich He is methyl or COOH and R4 is at least one of a group consistingof hydrogen, alkyl, alkoxy, halogen, sulfonic acid and car-boxyl.

The compounds represented by X are any diamino phenoxy compoundsrepresented by the formula HaN NH:

1! 1 11 in which -(CM2)m4 represents the group consisting of straightand branched chain aliphatic radicals wherein M occurs twice asindicated and the symbol M represents like and unlike members of thegroup consisting of hydrogen and alkyl radicals containing 1 to 6carbons. Of these radicals there may be 1 to 10 as indicated by thesubscript m. For example, -(CM2)m includes such radicals as CHz,-CI-hCHz-CHz-,

In these radicals alkyl may be any saturated aliphatic hydrocarbonradical containing 1 to 6 carbons such as -om, CHCH3, 41-0213 and-CCHCH;

CHr-CHz on; em

in which B occurs twice and represents like and unlike members of agroup consisting of hydrogen and straight and branched chain aliphaticgroups having 1 to 6 carbons, and in which there I may be 2 to 10 ofthese radicals as indicated by.

the symbol n; diamino cycloalkanes having 4 to 6 carbons in the ring andthe straight and branched chain saturated aliphatic derivatives thereofin whichathe substituent groups have 1 to 6 carbons; and cyclicdi-imines having 3 to 6 carbons inthe ring and the straight and branchedchain saturated aliphatic derivatives thereof in which the substituentgroups have 1 to 6 carbons.

The invention will be more fully, set forth in the following moredetailed description which includes examples that are given asillustrative embodiments of the invention and not as limitationsthereof, Parts are given in parts by weight.

Example 1 A slurry was made of 143 parts of l,2-di(4'-amino-phenoxy-acetyl-amino)ethane in 2,000

benzoyl-amino) naphthol-Y-sulfonio-acid in NaOaS N- G 2,000 parts ofwater and an aqueous solution of ammonia was added in sufiicientquantity to make a complete solution and a slightly alkaline reaction toBrilliant Yellow Paper. Then '7 parts of sodium-bicarbonate were added,the solution was cooled to 0 C. and 170 parts of sodiumcarbonate wereadded.

The tetrazo was slowly added to the cold alkaline solution of2(3-amino-benzoyl-amino)- 5-naphtho1-7-sulfonic-acid whilst maintainingan excess of the coupling component and alkalinity with sodiumcarbonate. The mixture was stirred one hour after the addition of thetetrazo, then the suspension was heated to 0., salted 5% with sodiumchloride and iiitered.

The filter cake was slurried with 3,000 parts of water to a smoothslurry and 91 parts of hydrochloric acid were added as a 30% solution.Tetrazotization was carried out at 10-12 C. for one hour.

The tetrazo was slowly added to the cold alkaline solution of1,3dihydroxy-benzene, stirred one hour after the addition, heated to60-70 C., salted 5% with sodium chloride, filtered and dried at 80-85 C.in an oven. The dry powder had an orange appearance.

The compound is represented by the formula The rinsed dyeing from theabove operation was entered into 500 cc. of water at -140 F. andapproximately10 cc. of 10% formaldehyde (25 cc. of approximately 37%formaldehyde by weight diluted to 250 cc. with water) were added. Thedyeing was held in this solution and at this temperature for twentyminutes. The dyeing was then removed, rinsed and dried.

An alternative after-treating process which is the preferred procedurebecause of its economy and ease of application is carried out by addingto the dyebath at the end of the dyeing period 10 cc. of 10%formaldehyde at bath temperature. Then after twenty minutes, the dyeingis removed, rinsed and dried.

A dyeing with a bright yellow scarlet shade was obtained which showedexcellent fastness to washing and good discharge properties.

Example 2 A tetrazo from 143 parts of 1,2I-di(..'-aminophenoxy-acetyl-amino) ethane was prepared as described inExample 1.

A solution was preparedirom 4,000 parts of water, 185 parts of1(3-amino-phenyl),-5-pyrazolone-3-carboxylic-acid, and 80 parts ofsodiumcarbonate was prepared and then 210 parts or sodium carbonate wereadded. The solution was cooled to-0-5 C. and the tetrazo was slowlyadded to the cold alkaline solution of 1 (3'-aminophenyl)-5-pyrazolone-3-carboxylic-acid. An excessof the coupling component andsodium carbonate alkalinity was maintained and the mixture was stirredone hour after the addition of the tetrazo was added. The resultingsuspension I a i c Orv-m- SOzNa N N i ll II N Q O OH- OH As illustrativeof the manner of using the compounds of the invention, a dyebath wasmade by dissolving 0.4 g. of the above described product in 100 cc. ofwater at 190-200 F. and adding 0.2 g. of sodium carbonate to assist thesolution. The solution was diluted with stirring to a total volume 01500 cc. with water at approximately F. and 40 cc. of a 10% solution ofGlaubers salt were added. A 10 g. piece of regenerated cellulose fiberwas wet out with water, squeezed partially dry and entered into thedyebath. The temperature of the dyebath was raised to F. in the courseof fifteen minutes and held at that temperature for one hour withstirring at frequent intervals this time. At the end of one hour thedyeing was removed and rinsed in cold water.

was heated to 10-80 C., and finally salted 5% with sodium chloride andfiltered.

The filter cake was slurried with 3,000 parts of water to a smoothslurry and 91 parts of 100% hydrochloric acid were added as a 30%solution. The mixture was cooled with ice to 10 C. and 55 parts of 100%sodium nitrite were added as a 30% solution. Tetrazotization was carriedout at 105-12" C. for one hour.

A mixture was made by stirring 105 parts of '1.3-dihydroxy benzene into2,000 parts of water. The mixture was cooled to 0 C. and 212 parts ofsodium carbonate were added.

The tetrazo was slowly'added to the cold alkaline solution of1,3-dihydroxy-benzene, stirred one hour after the addition and thenheated to 60-70 C. The suspension was salted 5% with sodium chloride,filtered and dried at 80-85 C. The products of the followingillustrations were in an oven. The dry powder had a yellow orangeprepared by methods similar to the foregoing.

appearance and is represented by the formula u if NaO O C("3-CH-N=NC OCHzC-NHCHzCHzNHC-CH2OON=NCHfiC O ONa N /(B=O 0=$ N on B By dyemg andafter-treatmg in a manner 51mllar to that described in Example 1, adyeing with The most applicable method of preparation W111 a. brightyellow orange shade was obtained which be easily ascertamable from theforegoing illusshowed excellent fastness to washmg. trations by thoseSkilled 1n the art.

Example Combination Shade 1,2,di 4'-a1nino-2-sulfophenoxyacetyi-amino)ethane =3 (2-amino-5-naphthol-7-sulfonic Red.

acid 1 =3 (1,3Fdihydroxy benzene.1,2rdi(4'-amino-phenoxy-acetyl-amino)ethane =3(2-amino-5-naphthol-7-su1fonic acid); Bordeaux.

(LB-dihYGI'OXY-MDZQHQZ- n 1,2-di(4-amino-phenoxy-acetyl-amino)ethane =32(4-am1no-3'-sul1o-phenyI-aminc)5- Maroon. o0 naphthol-7-sulfonic-acidz=3 (1,3-dihydroxy-benzene)z.

1,2-di(4-amindT-suHOphenoXyacetyIamino)ethane =32(3-am1nobenzoyl-ammo)-5- Orange.

naphthol-7-sulfonic acid: (l,3-dihydroxy-benzene)z.1,2-di(4-amin0-2-sulfophenoxyacetyi-amino)ethane =32(4-aminobenzoyi-amino)-5- Do.

naphthoi-7-sulionic acid: =3 (1,3 dihydroxy-benzene) z.1,Z-di(4-amino-2-suliophenoxyacetyl-amino)ethane =31(3-aminopheny1)5-pyrazolone- Yellow.

3-carboxylie acid; (1,3-dihydroxy-benzene)-.-. nl,2-d1(4-amino-2-ulfophenoxyacetyl-amino)ethane =3 2(4'-am1n0-3-sulfophenylam1no)-Maroon. am hthol-7-sulfonic acidi=3 (1,3-dihydroxy-benzeneh.

1,2-d i 4-amino-2'-suliophenoxyacetyl-amino)ethane =3(l-ammonaphthalene-fi-sulfonrc Brown. acid): =3(1,3-dihydrox'y-benzeneh. i1,2-di(4'-amino-2'-methoxyphenoxy-acetyl-amino)ethane =3 2(3-arninobenzoyl amino)- Scarlet.

fi-n aphthol-7-sulfonic acidz =3 (1,3-dihydroxy benzeneh. 1,2'd1(4'-amino-2'-methoxyphenoxy-acetyl-amino)ethane =3(2-am1no-5-naphthol-7-sul- Maroon. ton c acid): -3 (1,3-dihydroxybenzeneh. 40 1,2'-di(3'-amino-2-methylphcnoxyacetyl-amino) ethane =31-(3-aminophenyi)-5-pyrazo- Yellow.

lone-3-carboxylic acid =3 (1,3-dihydroxy-benzeneh.1,2-d1(3-amino-2-methylphenoxy-acetylamino) ethane =32-(3'ammobenzoy1am1no)-5 Orange.

naphthol 7-sulfonic acid: =3 (1,3-dihydroxy-benzene) z. 1,2-di3'-amino-2-Inethylphenoxyacetyl-amino) ethane =3(2-amino-5-naphthol-7-sulfon1c Maroon.

acid 2:; (1,3-dihydroxy-benzeneh. c1,2-di(3-aminc-2methylphenoxy-acetylamino) ethane =3(1-am1no-5naphthol-7-sulfonic Do. 4 5 acid): 3 (l,3-dihydroxy-benzene)a.

1,2-d1(3-amino-2-methylphenoxy-acetylamino) ethane =32-(4-am1no-3'-snifophenyl- Rubme amino)5-naphthol-7-su1l'onic acid, =3(1,3-di-hydroxy-benzeneh. 1, 2-di(3' arninophenoxyacetylamino) ethane =32-(3-aminobenzoylamino)5-naphthol-7- Orange.

suilonic acid: =3 (1,3-dihydroxy benzene) 1.1,2di(3-aminophenoxyacetylamino) ethane =3 (2-ammo-5-naphthoi-7-sulfonic801d): Maroon.

=3 (1,3-dihydroxy-benzeneh. 51,2-di(4'-amino-2chlorophenoxy-acetylamino) ethane =32(3'aminobenzoylammo)5- Scarlet.

0 naphtholJ-sulfonic acid; =3 (ha-dihydroxy-benzeneh.

1,2-d (4-amino-2 chlorophenoxyacetylamino) ethane =3(2-ammo-5-naphthol-7-sulfonic Maroon. y acid): =3(1,3-dihydroxy-benzeneh.

i,2-d1(4aiangfo-2gulfophenoxyacetyl-amino) ethane =3(i-aminonaphthalene), =3 Brown.

y oxyenzene 1,2-di(4-amino-2-sulfophenoxyacetylamino) ethane =3(2-methoxy-5-methylan lme)z Do.

=3 (1,3-dihydroxy-benzeneh. 1,2-di(4'-aminophenoxyacetylamino) ethane 32(4"(4'-aminobenzoyi) aminobenzoyia- Scarlet.

mino)-5-naphthol-7-sull'onic acid: =3 (1,3-dihydroxy-benzene)1,2-di(4-amino&henoxyacetylamino)ethane =3(l-ammonaphthaicnc-fi-sulfonic 801d): Brown.

=3 (1,3-d ydroxy-benzeneh. V 1,2-di(4-aminophenoxyacetylamino)ethane =3(l-amino2-mcthoxy-naphthalenc-(i-sul- Do.

Ionic acid); =3 (1,3-dihydroxy-benzeneh.1,2-di(4-aminophenoxyacety1amino)ethane =3(l-am1no-8-naphthol-3,6-d1sulionic acid): D0- =3(1,3-dihydroxy-benzeneh. 1,G-di(4-aminophenoxyaeetylamino)hexane =3[1-(3-am1n0phenyl)5-pyrazoloneQ-car- Orange.

boxylic acid]; =3 (1,3-dihydroxy-benzene)z. l,6-di(4-aminohenoxyacetylamino hexane =3 [2-(3-am1nobenz0y1armno)5-naphthol-7-Scarlet.

Sulfonic acid 2 =3 (1,3-dihydroxy-benzeneh. 1,6 di( 1aminophenoxyacetylamino) hexane =3 (2 amino 5 naphthol 7 sulfonic M rooacid) (1,3-dihydroxy-benzeneh. 1,6 di(4' aminophenoxyacetylamino)hexane=3 (1 amino 5 naphthol 7 sulfomc D0. acid), 3 (1,3-dihydroxy-benzeneh. V1,6-di(4-arninophenoxyacetylamino) hexane =3[2-(4'amino-3-sulio-phenylamino) -5-naph- Rubmo. thol-7-sulfonic acidh(1,3-dihydroxy-benzeneh.

1,2-di(4-amino henoxyacetylamino)ethane =3[2-(3-ammobenzoylamino)5-naphthol-7- Scarlet.

sulfonic acid 1 =3 (1,3-dihydroxy-5-methyl benzene. l,2-di(4-aminohenoxyacetylamino)ethane =3 [2-g3-ammobenzoylammo-5-naphthol'7- D0.

sulfonic acid a=3 (1,3dihydroxy-benzene-5-sulfomc acid )z.1,2-di(4-amino henoxyacetylamino)ethane =3[2-(3@ammobenzoylaminot-naphtho1-7- D0. sulfonic acid 2 =3(1,3,5-trihydroxy-benzene) Di-(4-amino-phenoxy-acetyl)piperazine =3(2-(4-arnino-3-sulfo-phcnyl-amin0)5-naph- Red violet.

thol-7-sulfonic acid); (1.3-dihvdroxy-benzene);Di-(4-amino-phenoxy-acetyl)piperazine =3 (i-ammo-5-naphthol-7-sulfon1cacid): =3 Maroon.

(1,3-dihydroxy-benzeneh. Di-(4-amino-phenoxy-acetyl)piperazme =3(2-amino-5-naphtho1-7-suli0nic ac1d);-=-=3 Red violet. (1-3-dihydr0xy-benzene)g. 7 Di-(kamino-phenoxy-acetyl)piperazme =3(1-(3'-amino-phenyl)5-pyraz01one-3-carbcxy: Orange.

lic acid); =3 (1,3'dihydroxy-benzene) Example Combination Shade 40Di-(4-amino-phenoxy-aoetyl)-piperazine =3 (z-amino-5-naphtbol-l-sulfonicacid); =3 Bordeaux. 5 (l S-dihydroxy-bonzeneh.

41 Di-(4-amino-phanoxy-acetyl)- iperazine =3 (2--amino-benzoyI-amino)-5-naphth0l-7- Scarlet.

sulionic acid); =3 (1,3 ydroxy-benzeneh. 421,4-di-(4-amino-phenoxy-acetylami; 2-cyclohexane =3(l-(3-amino-phenyl)-5-pyrazo- Yellow.

lone-a-carboxylic aeid),=3 (1, ihydroxy-benzeneh. 43 l,4di4'-amino-phenoxy-aeatylamino)-cyclohexane =3 (2-(3-aminobenzoylamino)-5-Scarlet.

nap thol-7-sulfonic acid); =3 (1,3dihydroxy-benzene)g. m 441,2-di(2-amino-phenoxy-acetylamino)ethane =3[2-(3-aminobenzoylammo)-5-napbthol- D0.

7-suli0nic acid], =3 (1,3-dihydroxy-benzene) z. 45l,Z-di(2-amino-phenoxy-acetylamino)ethane =3 [l-(3-aminophenyl)-5pyrazo1one-3-car- Orange.

boxylic acid]; =3 (1,3-dihydrxy-benzeneh.

As representative of the many compounds 15 which may be used as Acomponents are mentioned 1,3-dihydroxy benzene, 1,3-dihydroxy-- methylbenzene, 1,3-dihydroxy-5-isoprop'yl benzene, 1,3-dihydroxy-5-hexylbenzene, 1,3-dihydroxy-5-benzene sulfonic acid, 1,3-dihydroxybenzene-S-carboxylic acid, 1,3,5-trlhydroxy benzene,1,3-dihydroxy-5-methoxy benzene, 1,3-di-' hydroxy 5-ethoxy benzene, 1,3-dihydroxy-5- hexoxy benzene, 1,3-dihydroxy-5-amino benzene and1,3-dihydroxy-5-benzo-nitrile.

Representative of Y components are: aniline, 3-amino toluene,2,5-dimethoxy aniline, 2-methoxy aniline, 2-methoxy-5-methyl aniline; 1-amino naphthalene, 1-amino-2-methoxy-naphthalene,1-amino-naphtha.1ene-fi-sulfonic acid, 1- 30 amino-z-methoxynaphthalene-G-sulfonic acid,

l-amino-naphthalene-G-carboxylic acid, l-amino-7-methoxy naphthalene,1-amino-7-chloronaphthalene; 1,8-amino naphthol-3,6-disulfonic acid,2-amino-8-naphthol-3,6-disulfonic acid, 1-amino-B-naphthol-4,6-disulfonic acid, l-amino-8-naphthol-3,5-disulfonic' acid, 1-amino-8 naphthol-i-sulfonic acid,1-amino-5-naphthol-7- sulfonic acid, Z-amino-5-naphthol-7-sulfonic acid,2-amino-8-naphthol-6-sulfonic acid, 1- o amino-5-naphthol; 2-(4' aminobenzoyl amino) -5-naphthol 7 sulfonic acid, 2-(3'-amino benzoyl amino)-5-naphthol-7-sulfonic acid, 1 -(4'- amino benzoyl amino) 5 naphthol-7-sulfonic acid, 2[4-(4"-amino benzoyl ami- 45 no) benzoyl amino] 5naphthol 7 sulfonic acid, 1-(4'-amino benzoyl amino)-8-naphthol-4-sulfonic acid; 1-(3'-amino phenyD-5-pyrazolone-3-carboxyllc acid, 1-(4-amino phenyl)-5-pyrazolone-3-carboxylic acid, 1-(3'- 50 aminophenyl)-3-methyl-5-pyrazolone, 1-(4'- aminophenyl)-3-methyl-5-pyrazolone, 1-(2- niethoxy-5-amino phenyl)-3-methyl-5-pyrazolone, 1- (4-amino-3-carboxy) -3-methyl-5-pyrazolone,1- (4'-amino-3-carboxy) -3-m ethyl-5- 55 pyrazolone, 1-(4'-amino-3'-sulfo) -5-pyrazolone- 3-carboxylic acid,'1(2-methyl-5'-amino phenyl) 3-methyl-5-pyrazolone, 1(2-methyl-5'-aminophenyl) -5-pyrazolone-3-carboxylic acid and 1- (2'-chloro-5'-aminophenyl) -5-pyrazolone-3- 5o carboxylic acid.

Representative of the many X components are:1,2-di(4-aminophenoxyacetylamino) ethane, 1,6- di (4'-aminophenoxyacetylamino) hexane, 1,10-di-(4'-aminophenoxyacetylamino)decane, 1,2-di 65(3'-aminophenoxyacetylamino)ethane, 1,3-di(4- aminophenoxyacetylamino)propane, 1,2-di(4'- aminophenoxyacetylamino) -1,2-dimethyl ethane,1,2-di(alpha-4-amino-phenoxypropionylamino) ethane,1,2-di(beta-4'-aminophenoxypropionyl- 70 amino) ethane,1,2-di(4'-amino-2-methoxyphenoiwacetylamino) ethane, 1,2-di-( 2-methyl-5' aminophenoxyacetylaminolethane, 1,2-di(2'-chloro-i-aminophenoxyacetylamino) ethane, 1,3- di (alpha-4-aminophenoxy-butyryl-amino) -pentane,1,4-di(alpha-ethyl-beta-3'-amino-phenoxypropionylamino)-4-methyl-3-ethyl-pentane,di- (4-aminophenoxyacetyl) -piperazine, 1,4-di (4-aminophenoxyacetylam'lno) -cyclohexane, 1,4-di-(4-aminophenoxyacetylamino) -cyclobutane, 1,4-dit4-aminophenoxyacetylamino) -dimethyl-cycloh e x a. n edi(4-aminophenoxyacetyl) -methylpiperazine, 1-,2-di(3'-amino-phenoxyacetyl) -3,5- dimethyl pyrazolidine,1,2-di(3'-amino-phenoxyacetyl) -2 ,5-dimethyl piperazine,1,4-di(4'-aminophenoxyacetyl)-ethylenertrimethylene diamine.

The preferred embodiments of the invention are those in which the Acomponent is resorcinol and the Y component is one of theamino-phenylpyrazolone or one of the amino-naphthol radicals of thekinds described. Of these the embodiments where Y is one of theamino-naphthol radicals are preferred.

Deeper shades than the direct or formaldehyde treated dyeings and withbetter light fastness are produced by after-treatment of these colorswith water-soluble metal salts, such as watersoluble saltsof copper, forexample copper sulfate. For example, the af-ter-coppering operation maybe carried out by either of the procedures outlined in Example 1 for theafter-treatment with formaldehyde, by using instead of formaldehyde asolution containing a 5% solution of hydrated cupric sulfate equal inamount to the formaldehyde used in the preceding step. In all cases thoperation is allowed to continue for twenty minutes, or for such othertime as is necessary to metallize the dyeing, at the end of which timethe treated dyeing-s are removed,

rinsed and dried. The after-coppering may replace the formaldehydetreatment, but both aftertreatments are preferred where the .best lightfastness as well as washing fastness is desired. After-treatment withboth formaldehyde and metal salts may be done either in the dye bath orin a fresh bath. When a fresh formaldehyde bath is used and the dyeingis treated for a sufilcient time to form the formaldehyde compound,themetal salt may be added and the treatment continued for an intervalof time. Thedyeings are then removed, rinsed and dried. Similar resultsare obtained by reversing the order of adding the after-treatingreagents, that is, by adding the metal salt solution first, treating forthe necessary time, and then adding the formaldehyde solution. Aftertreating the dyeing for about twenty minutes, it is removed, rinsed anddried.

The described method of dyeing is typical but it is to be understoodthat the invention is not restricted to the precise concentration-s,temperatures and intervals of treatment specified in the examples sincethese details can be variously modified as will'be understood by thoseskilled in the art. For example, the after-treatments with formaldehydeor metal salts may be carried on for longer or shorter periods and athigher or lower temperatures than those specified in the illustrations.Any treatment which will form a formaldehyde complex with th dyeing orone of the described metal complexes with the dyeing, as the case maybe, produces the improved results with the dyes described. The exactcomposition of the described formaldehyde and metal complexes is unknownto me, but from my investigations it is my present belief thatformaldehyde and metal complexes are formed.

Any of the halogens may be present as substituents where indicated. Thesulfonic acid and carboxyl groups in the finished dyes may be the saltsof any of the alkali metals and are produced by using bases of otheralkali metals in the process instead of sodium. The acid forms of thefinished dyes can be made by subjecting them to acids by methodswell-known to the art.

The compounds of the invention in the form of their alkali metal saltsgive dyeings on cotton and similar dye susceptible fibers which areequal to or superior in washing fastness to the developed colors. Thedyeings compare favorably in brightness with direct colors having otherdiamino diaryl nuclei but their washing fastness is of a superior order.The processes of applying the dyes of the invention are simple tooperate. since it is possible to make a complete dyeing in one bath.Thus the dyes of the invention comblue the economy and simplicity ofoperation attainable with the use of direct dyes with the superiorwashing fastness which is attainable with developed dyes which requiregreater eflort and expense on the part of the dyer.

Water-soluble metal salts of various metals can be used for metallizingthe dyeings, those having atomic weights between 50 and 65 being themost suitable. As examples of such metals copper, chromium, nickel,cobalt and iron are mentioned. Either water-soluble salts of inorganicor organic acids can be used such as sulfates, halides, formates andacetates, for example co per sulfate, nickel sulfate, chromium chloride/copper formate, copper acetate and many other watersoluble metal saltsof inorganic and organic acids. I

Since from the foregoing description of the invention it will beapparent to those skilled in the .art that the invention is susceptibleof modification, it is to be understood that the invention is notlimited to the specificillustrative embodiments.

I claim: 1. The tetrakisazo dyestuffs which in their acid form arerepresented by the formula sulfonic acid and carboxyl; CM: is a groupconsisting of straight and branched chain aliphatic radicals wherein Moccurs twice and is one of a group consisting of hydrogen and straightand branched chain alkyl having 1 to 6 carbon atoms m is an integer notgreater than 10; D is the radical of a group consisting of straight andbranched chain aliphatic diamines having a formula NHz-(CBaM-NH: whereinB occurs twice and is one of a group consisting of hydrogen andaliphatic radicals having 1 to 6 carbon atoms and n is'an integer 2 to10, diamino cycloalkanes having 4 to 6 carbons in the ring and the 1- to6-carbon saturated aliphatic derivatives thereof, and di-imino cycliccompoundshaving 3 to 6 carbons in the ring and the 1- to 6-carbonsaturated aliphatic derivatives thereof; each Y is the radical aftercoupling and azotization of a compound of the group consisting of thel-(amino phenyl) pyrazolones and compounds of the benezene andnaphthalene series which are represented by the formulae wherein R2 isone of a group consisting of methyl and carboxyl; R3 is at least one ofa group consisting of hydrogen, alkyl and alkoxy having 1 to 6 carbons;R4 is at least one of a group consisting of hydrogen, alkyl, alkoxyhaving 1 to 6 carbons, sulfonic acid and carboxyl; R5 is one of a groupconsisting of hydrogen and sulfonic acid and -0H and SO3H are separatedin the naphthalene nucleus by at least one unsubstituted position; R6 isone of a group consisting of sulfonic acid and carboxyl; and Z is one ofa group consisting of amino and amino benzoylamino of the formula z NHCO2 2. The tetrakisazo dyestuffs whichin their acid form are representedby the formula H wherein R is at least one of the group consisting ofhydrogen, straight and branched .chain alkyl having 1 to 6 carbons, thecorresponding alkoxy groups, ary1-, aryl-alkyl-, halogen, CN, sulfonicacid and carboxyl; CM: is a group consisting of straight and branchedchain aliphatic radicals wherein M occurs twice and is oneof a groupconsisting of hydrogen and straight andbranched chain alkyl having 1 to6 carbon atoms; m is an integer not greater than 10; D is the radical ofa group consisting of straight "and branched chain aliphatic diamineshaving a formula NH2(CB2)n-NH2 wherein B occurs twice and is one of agroup consisting of hydrogen and aliphatic radicals having 1 to 6 carbonatoms and n is an integer-2 to 10, diamino cycloalkanes having 4 to 6carbons in the ring and the 1- to S-carbon saturated aliphaticderivatives thereof, and di-imino cyclic OH 803K compounds having 3 to 6carbons in the ring and the 1- to 6-carbon saturated aliphaticderivatives thereof; each Y is the radical after coupling andazotization of a compound of the group consisting of the l-(aminophenyl) -pyrazolon'es and compounds of the benzene and naphthaleneseries which are represented by the formulae wherein R2 is one of agroup consisting of methyl and carboxyl; R3 is, at. least one of agroupconon V sisting of hydrogen, alkyl and alkoxy having- 1 to 6 carbons; R4is at least one of a group consisting of hydrogen, alkyl, alkoxy having1 to 6' carbons, sulfonic acid and carboxyl; R5 is one of a groupconsisting of hydrogen and sulfonic acid and OH and SO3H are separatedin the naphthalene nucleus by at least one unsub-' stituted'- position;R is one of a group consisting of sulfonic acid and carboxyl; and Z isone of a group consisting of amino and amino benaoylamino of the formula1 containing not more than two benzene nuclei and having one primaryamino group meta or para to CO-. V

3. The azo compounds which in the form of their acids are represented bythe formula 0 O NH:

wherein R is one of a group consisting of hydrogen, straight andbranched chain alkyl having 1 to 6 carbons, the corresponding alkoxygroups, hydroxy, amino, CN, halogen, sulfonic acid and carboxyl; R is atleast one of the group consisting of hydrogen, straight and branchedchain alkyl having 1 to 6 carbons, the corresponding,. alkoxy groups,aryl-, aryl-alkyl-, halogen, CN, sulfonic acid and carboxyl; CMz' is agroup consisting of straight and branched chain aliphatic radicalswherein M'occurs twice and is one of a group consisting of hydrogen andstraight and branched chain alkyl'having 1 to 6 carbon atoms; m is aninteger not greater than 10; D is the radical of a group consisting ofstraight and branched chain aliphatic diamines having a formulaNHz-(CBz) n-NI'IZ wherein B occurs twice and is one of a groupconsisting of hydrogen and aliphatic radicals having 1 to 6 and the 1-to 6-carbon saturated aliphatic derivatives thereof, and di-imino cycliccomf pounds having 3 to 6 carbons in the ring and the 1- too-carbonsaturated aliphatic derivatives thereof; R is one of a group consistingof hy-- drogen and sulfonic acid; OH and SOsH are separated in thenaphthalene nucleus by at least one unsubstituted position and Z is oneof a group consisting of amino and amino benzoylam'ino of the formulacontaining not more than two benzene nuclei and having one primary aminogroup meta or fpara to g v 4. The aim compounds which in the form oftheir acids are represented by the formula v in which R is one of agroup consisting of hy- EQN o l drogen, straight and branched chainalkyl having 1 to 6 carbons, the corresponding alkoxy H II I ll chainaliphatic diamines having a formula NHe-(CBzM-NHz wherein B occurs twiceand is one of a group consisting of hydrogen and aliphatic radicalshaving 1 to 6 carbon atoms and n is an integer 2 to 10, diaminocycloalkanes having 4 to 6 carbons in the ring and the 1- to 6-carbonsaturated aliphatic derivatives thereof, and di-imino cyclic compoundshaving 3 to 6 carbons in the ring and the 1- to fi-carbon saturatedaliphatic derivatives thereof.

5. The compounds represented by the formula in which Q is an alkalimetal;

6. The compounds represented by the formula I M 0 H in which Q is analkali metal.

'7. The compounds represented by the formula wherein R2 is one of agroup consisting of methyl I QOaS N=NO01I O O NH:

t 1'1 wherein R is at least one of the group consisting of hydrogen,straight and branched chain alkyl having 1 to 6 carbons, thecorresponding alkoxy groups, ary1-, aryl-alkyl-, halogen, CN,

r sulfonic acid and carboxyl; CMz is a group consisting of straight andbranched chain aliphatic radicals wherein M occurs twice and is one of agroup consisting of hydrogen and straight and branched chain alkylhaving 1 to 6 carbon atoms; m is an integer not greater than 10; D isthe radical of a group consisting of straight and branched chainaliphatic diamines having a formula NHz(CBz)1rNH-z wherein 3 occurstwice and is one of a group consisting of hydrogen and aliphaticradicals having 1 to 6 carbon atoms and n is an integer 2 to 10, diaminocycloalkanes having 4 to 6 carbons in the ring and the 1- to 6-carbonsaturated aliphatic derivatives thereof, and di-imino cyclic compoundshaving 3 to 6 carbons in the ring and the 1- to 6-carbon saturatedaliphatic derivatives thereof; coupling said compound in alkaline mediumwith one of a group consisting of the l-(amino phenyl) pyrazclones andthe compounds of the benzene series which are represented by theformulae HOON=N so3 and carboxyl; R3 is at least one of a groupconsisting of hydrogen; alkyl and alkoxy having 1 to 6 carbons; R4 is atleast one of a group consisting of hydrogen, alkyl, alkoxy having 1 to 6carbons, sulfonic acid and carboxyl; R5 is one of a group consisting ofhydrogen and sulfonic acid and OH and --SO3H are separated in thenaphthalene nucleus by at least one unsubstituted position; R6 is one ofa group consisting of sulfonic acid and carboxyl; and Z is one of agroup consisting of amino and amino benzbylamino of the formulacontaining not more than two benzene nuclei and having one primary aminogroup meta or para to CO; tetrazotizing the disazo compound thusobtained and coupling in alkaline medium with a meta-dihydroxy-benzenewhich is represented by the formula in which R is one of a groupconsisting of hydrogen, straight and branched chain alkylhaving 1 to 6carbons, the corresponding alkoxy groups, hydroxy, amino, CN, halogen,sulfonic acid and carboxyl.

14. The process which comprises dyeing a dyeable fabric with a compoundin accordance with claim 1; and then applying aqueous formaldehyde untila formaldehyde complex is formed.

CHILES E. SPARKS.

